EP0152632A2 - Film poreux électroconducteur et procédé de fabrication - Google Patents

Film poreux électroconducteur et procédé de fabrication Download PDF

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Publication number
EP0152632A2
EP0152632A2 EP84116451A EP84116451A EP0152632A2 EP 0152632 A2 EP0152632 A2 EP 0152632A2 EP 84116451 A EP84116451 A EP 84116451A EP 84116451 A EP84116451 A EP 84116451A EP 0152632 A2 EP0152632 A2 EP 0152632A2
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EP
European Patent Office
Prior art keywords
polymer
porous film
electroconductive
aniline
oxidation
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP84116451A
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German (de)
English (en)
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EP0152632B1 (fr
EP0152632A3 (en
Inventor
Shohei Tamura
Sadamitsu C/O Nitto Electric Ind. Co. Ltd. Sasaki
Takeshi C/O Nitto Electric Ind. Co. Ltd. Sasaki
Hisashi C/O Nitto Electric Ind. Co. Ltd. Ichinose
Keiji C/O Nitto Electric Ind. Co. Ltd. Nakamoto
Masao C/O Nitto Electric Ind. Co. Ltd. Abe
Hitoshi C/O Nitto Electric Ind. Co. Ltd. Nakazawa
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Nitto Denko Corp
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Nitto Denko Corp
Nitto Electric Industrial Co Ltd
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Priority claimed from JP58252135A external-priority patent/JPS60145395A/ja
Priority claimed from JP412284A external-priority patent/JPS60148012A/ja
Priority claimed from JP412184A external-priority patent/JPS60148011A/ja
Priority claimed from JP23184884A external-priority patent/JPS61108644A/ja
Application filed by Nitto Denko Corp, Nitto Electric Industrial Co Ltd filed Critical Nitto Denko Corp
Publication of EP0152632A2 publication Critical patent/EP0152632A2/fr
Publication of EP0152632A3 publication Critical patent/EP0152632A3/en
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Publication of EP0152632B1 publication Critical patent/EP0152632B1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates to a novel electroconductive porous film and a process for producing same.
  • a conductive sheet by mixing conductive amorphous carbon, graphite, metal powder, or the like with rubber or resin, and molding the mixture by extrusion, compression, rolling, or other techniques, or, alternatively, by depositing a conductive metal on the surface of a rubber or resin sheet by vacuum vapor deposition, sputtering deposition, etc.
  • the sheet is generally insulating in the thickness direction.
  • the deposition thickness of the conductive metal must be limited in order that the flexibility of the support sheet may be retained, with the result that the electroconductivity of the product sheet is also limited to within a certain range.
  • aniline black Some of the products of the oxidative polymerization of aniline, e.g., aniline black, have long been known. Particularly, as an intermediate-in the production of aniline black, the octamer of aniline represented by formula (I) has been identified as emeraldine (A.G. Green et al., J. Chem. Soc., Vol. 97, p. 2388 (1910), ibid., Vol. 101, p. 1117 (1912)). This octamer is soluble in 80% acetic acid, cold pyridine, and N,N-dimethylformamide. The emeraldine is oxidized in an ammoniacal medium to form niqraniline, represented by formula (II), which is also known to possess solubility similar to that of emeraldine.
  • formula (II) niqraniline
  • this invention has as its object to provide a novel electroconductive porous film by direct deposition of a novel electroconductive organic polymer on a porous substrate film.
  • the present inventors extensively studied the conditions necessary for the manufacture of a dasirable eleotroconductive porous film, and found that the aforementioned oxidation polymer of aniline is a substantially linear high polymer comprising a quinonediimine structure as a main repeating unit and that a conductive porous film which is highly electroconductive, and which, when the substrate porous support is flexible, retains that flexibility, can be easily manufactured by a process in which the afore-mentioned electroconductive oxidation polymer of an aniline compound as obtainable with a chemical oxidizing agent is directly deposited on a porous substrate film, by a process in which said electro-oxidation polymer of aniline compound is deposited on a porous substrate film using the latter as a positive electrode, or by a combination process thereof.
  • the electroconductive porous film according to this invention comprises a porous substrate film having deposited thereon an electroconductive polymer containing an electron acceptor as a dopant, said polymer being a substantially linear polymer having as a main repeating unit thereof a quinonediimine structure represented by formula (III). wherein R 1 and R 2 , which are the same or different, each represents a hydrogen atom or an alkyl group.
  • compensation refers to an operation in which carriers (i.e., electrons and positive holes) are removed from electroconductive polymers.
  • carriers i.e., electrons and positive holes
  • the carrier is an electron
  • an electron acceptor is employed to remove or compensate the electron.
  • compensation is carried out with an electron donor when the carrier is a positive hole, i.e., when a p-type semiconductor ig used. It is also possible to compensate semiconductors or elactrcconductive polymers by giving thereto and taking therefrom electrons electrochemically.
  • this electroconductive polymer can be obtained as an independent product by preparing an electroconductive porous film in accordance with the method described hereinafter and detaching the desired polymer from the substrate film or by polymerizing an aniline compound with a chemical oxidizing agent or under electro-oxidation conditions in the absence of a substrate or support.
  • aniline compound as used herein means aniline and alkylanilines having 1 or 2 carbon atoms in the alkyl moiety.
  • the electroconductiva oxidation polymer of an aniline compound according to this invention generally has an appearance of a green to blackish green color in a dry powdery form. Generally, this green color gains in brightness as the degree of electroconductivity increases. However, a shaped product of the polymer produced by compression molding generally has a glossy blue color.
  • the electroconductive organic polymer in the electroconductive porous film of the present invention obtainable by a chemical oxidation process described hereinafter is insoluble in water and virtually all organic solvents, but is normally slightly to partially soluble in 97% sulfuric acid.
  • the eloctroconductive organic polymer obtainable by the electro-oxidation technique described hereinafter is normally substantially insoluble even in 97% concentrated sulfuric acid but depending on reaction conditions used, can include a moiety which is slightly soluble in 97% concentrated sulfuric acid.
  • the solubility of the polymer in 97% concentrated sulfuric acid varies depending upon the method of the reaction and the conditions of the reaction used for the polymer formation.
  • the electroconductive organic polymer obtained by oxidative polymerization of an aniline compound with a chemical oxidizing agent generally has a solubility in the range of from 0.2 to 10% by weight, and in moat cases, in the range of from 0.25 to 5% by weight.
  • solubility as used herein, particularly with respect to polymer of high molecular weight, is to be interpreted to be such that polymer contains a portion having a solubility in the above-described range.
  • the polymer according to this invention thus sharply contrasts with emeraldine which is soluble, as described above, in 80% acetic acid, in cold pyridine, and in N,N-dimethylformamide.
  • the polymer of the present invention obtainable by the chemical oxidation, when dissolved in 97% concentrated sulfuric acid at a concentration of 0.5 g/dl (gram/deciliter), possesses a logarithmic viscosity number in the range of from 0.1 to 1.0, and in moat cases, in the range of from 0.2 to 0.6.
  • the term "logarithmic viscosity number" as used herein, particularly with respect to a polymer of high molecular weight, is to be interpreted so that the portion of the polymer soluble in 97% concentrated sulfuric acid falls in the range described above.
  • the logarithmic viscosity number (n inh) is wall known in the art and can be determined by the following formula: wherein:
  • the logarithmic viscosity numbers of emeraldine and aniline black determined under the same conditions are, respectively, 0.02 to 0.005, signifying that the polymer according to the present invention obtainable by the chemical oxidation has a high molecular weight.
  • the results of differential thermal analysis also indicate that the polymer according to the present invention obtainable by the chemical oxidation is a polymer having high molecular weight.
  • the electroconductive polymer prepared by the chemical oxidation process and that prepared by the electro-oxidation procass are in agreement with each other in infrared absorption spectrum and their elemental analyses also suggest that they have the same chemical structure. Therefore, the following discussion on the conductive polymer obtainable by the chemical oxidation process applies to the polymer obtainable by the electro-oxidation process as wall.
  • the infrared absorption spectrum of the electroconductive polymer according to this invention somewhat resembles that of emaraldine. However, in the infrared absorption spectrum of the polymer in this invention, the absorption due to the deformation vibration outside the C-H plane of a mono-substituted benzene clearly recognized in emeraldine is not substantially observed, and the absorption due to a para-substituted benzene is relatively high.
  • the absorption spectrum of the polymer in this invention differs widely from that of aniline black.
  • the polymer of the present invention accordingly, appoars to possess a somewhat emeraldine-lika structure, containing a number of para-substituted benzene rings.
  • the polymer in this invention is doped with an electron acceptor which is present in the polymerization system during the course of the oxidative polymerization of an aniline compound. As a result, it possesses high electroconductivity. In this polymer, therefore, electron transfers from the polymer to the electron acceptor and a charge transfer complex is formed between the polymer and the electron acceptor.
  • the polymer in this invention is molded in the shape of a disk, for example, and a pair of electrodes are fixed on the disk and a temperature differenca is produced between the electrodes to give rise to thermal electromotive force peculiar to a semiconductor, a positive electromotive force is generated on the electrode of the low temperature side, and a negative electromotive force on the electrode of high temperature side. This fact indicates that the polymer used in this invention is a p-type semiconductor.
  • the curve A represents the spectrum of the polymer in the unaltered form
  • the curve B the spectrum of the polymer in the chemically compensated form
  • the curve C the spectrum of the polymer in the doped form.
  • the spectrum of C agrees substantially completely with the spectrum of A.
  • Examples of the dopant which the electroconductive polymer in this invention can contain include halogens such as chlorine, bromine, and iodine, Lewis acids such as ferric chloride, tin tetrachloride, and copper dichloride, inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, and nitric acid, and organic acids such as picric acid, and p-toluenesulfonic acid.
  • halogens such as chlorine, bromine, and iodine
  • Lewis acids such as ferric chloride, tin tetrachloride, and copper dichloride
  • inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, and nitric acid
  • organic acids such as picric acid, and p-toluenesulfonic acid.
  • the foregoing list of dopants is only exemplary, and dopants useful according to the present invention are not limited thereto.
  • the chemical structure of the electroconductive polymer in this invention is confirmed by the elementary analysis of the polymer itself and also by the elementary analysis of the polymer produced by chemically compensating the original polymer with ammonia (hereinafter refar- red to as a "compensated polymer").
  • the polymer is a linaar high molecular polymer substantially of the above-described repeating unit (III). It is believed to acquire high electrcconductivity because the - electron conjugare system of the polymer contains the dopant.
  • the electroconductive organic polymer in this invention may contain, in conjunction with the above repeating unit of quinonediimine structure, a repeating-unit represented by formula (IV) which is a reduced form of formula (III), again wherein R 1 and R 2 , which are the same or different, each represents a hydrogen atom or an alkyl group.
  • the polymer containing such a reduced structure can be easily produced, for example, by partially reducing the polymer of this invention.
  • Aftar the polymar comprising a repeating unit of formula (IV) is produced by reduction
  • the electroconductive organic polymer in this invention can also be obtained by oxidizing and simultaneously doping the reduced polymer with an oxidizing agent which is effective as an electron acceptor.
  • the electroconductive organic polymer produced by the oxidativa polymerization of an aniline compound preferably comprises as the main repeating unit the above repeating unit (III). Since this polymer has already been doped with a protonic acid during the course of the oxidative polymerization, it possesses high electroconductivity without requiring an additional doping treatment, and the electroconductivity of the polymer is retained even when the polymer is left standing in the atomosphere for a long time. Compared with the doped electroconductive organic polymers heretofore known to the art, the polymer in this invention possesses high stability.
  • the processes for producing an electroconductive porous film in accordance with this invention will now be described in more detail.
  • the electroconductive porous film according to this invention can be produced by chemical oxidation, eleatro-oxidation or a combination thereof.
  • alkylanilines can be used as the aniline compound.
  • Preferred examples of the alkylanilinc include o-methylaniline, m-methylaniline, o-sthylanilina, and m-ethylaniline.
  • aniline and these alkylanilines aniline is particularly preferred since it produces a polymer of high electroconductivity.
  • the porous substrate film to be used in the deposition of a chemical oxidation polymer of an aniline compound should have sufficient porosity and wettability to be impregnated with a solution of the aniline compound or the water-soluble salt thereof.
  • a solvent capable of wetting the porous substrate film in dissolution of the aniline compound or the water-soluble salt thereof is another approach.
  • Another approach is that of imparting wettability to the substrate with respect to the aniline solution by carrying out a surface treatment such as sputter etching, irradiation with ultra-violet light or electron rays, corona discharge, alkali metal treatment, etc.
  • the film When the porous substrate film is sufficiently wettable with an aniline compound, for instance, the film may be directly impregnated with the aniline compound or a solution thereof in an organic solvent.
  • the substrate film When the substrate film is hydrophilic, it can be impregnated with an aqueous solution of a water-soluble salt of aniline.
  • hydrophilic salts of the aniline compound include, among others, the hydrochlorids, sulfate, perchlorate, nitrate, hydrobromide, boroflucride, fluorophosphate, etc.
  • the substrata film is not suffi- ciantly wettable with an aniline compound or an aqueous solution thereof, as it is in the case with a porous film of polytetrafluoroethylene, it is possible to dissolve the aniline compound or the water-soluble salt thereof in an organic solvent having affinity for poly- tetrafluoroethylane, such as ethanol, and impregnate the film with the resulting solution. If the solvent is oxidizable with the oxidizing agent in the impregnation of the substrata film with the solution of the aniline compound or the water-soluble salt thereof, it is preferable to dry the impregnated film to remove the solvent.
  • an organic solvent having affinity for poly- tetrafluoroethylane such as ethanol
  • porous substrate film there is virtually no limitation on the material of the porous substrate film, and it can be selected according to the intended use of the product electroconduetiva porous film.
  • ethylene-vinyl acetate copolymer, cellulose derivatives, ethylene-vinyl alcohol copolymer, fluorine-containing resins such as polytetrafluoroethylenc, polyvinylidene fluoride, etc., polysulfones, polyetharsulfones, polymides, polyamides, etc. may be mentioned by way of example.
  • an aniline compound or its water-soluble salt is impregnatad in a porous film and the thus-inpregnated porous film is subjected to oxidative polymerization with an oxidizing agent in a protonic acid-containing reaction medium to produce an electroconductive polymer in such a manner that the molar ratio of protonic acid/potassium dichromate in the reaction medium is adjustad to at least 1.2/1, and preferably from 2/1 to 50/1, thus obtaining an electroconductive porous film having an elnctroconductivity of at least 10 -6 S/cm.
  • the porous film carrying an aniline compound or a water-soluble salt thereof is immersed in an oxidizing aqueous solution containing a protonic acid and an oxidizing agent whereby the aniline compound is oxidation-polymerized by the oxidizing agent to deposit a conductive polymer on the porous film. Therefore, the conductive oxidation polymer is deposited on the surface of the porous film inclusive of the surfaces of the walls defining the pores of the film, thus providing a generally electroconductive porous film.
  • chromium oxide (IV) or a dichromate such as potassium dichromate, sodium dichromate, or the like is preferred. Particularly, potassium dichromate is desirable.
  • chromium oxidizing agents such as chromic acid, chromates, chromyl acetate, etc., and manganese oxidizing agents such as potassium permanganate, etc., can also be employed if desired.
  • Examples of the protonic acid which can be used include sulfuric acid, hydrochloric acid, hydrobromic acid, tetrafluoroboric acid (HBF 4 ), and hexafluorophosphoric acid (HPF 6 ), with sulfuric acid being most p referred.
  • sulfuric acid is most p referred.
  • a mineral acid is used for the formation of tho water-soluble salt of aniline compound, this mineral acid may be the same as or different from the above-described protonic acid.
  • reaction medium examples include water, organic solvents miscible with water, and organic solvents not miscible with water, and mixtures thereof.
  • the reaction medium to be used is generally water, an organic solvent miscible with water, or a mixture thereof which is capable of dissolving the water-soluble salt.
  • the reaction medium can be either an organic solvent miscible with water or an organic solvent not miscible with water which is capable of dissolving the aniline compound. It is important that the organic solvent to be used as the reaction medium should not be oxidized by the oxidizing agent used in the reaction.
  • Examples-of organic solvents miscible with water include carbon tetrachloride and hydrocarbons.
  • the concentration of the protonic acid in the aqueous solution of oxidizing agent is not particularly limited. Generally, however, this concentration is in the range of from 1 to 10 N.
  • the protonic acid may be impregnated together with aniline or the water-soluble salt of the aniline compound in the porous film prior to effecting the reaction.
  • the reaction temperature for the oxidative polymerization to deposit an electroconductive polymer on a porous film substrate according to the chemical oxidation is not particularly limited as long as it does not exceed the boiling point of the solvent to be used.
  • the electroconductivity of the oxidation polymer obtained tends to decrease with the increasing reaction temperature. From the standpoint to produce a polymer having a high alectrocoaductivity, the reaction temperature is desirably below room temperature.
  • the porous film having depositad thereon a polymer is poured into a large volume of water or an organic solvent, and is washed with water until the filtrate becomes neutral, washed with an organic solvent such as acetone until tha solvent is not colcred, and vacuum dried to obtain an electroconductive porous film according to chemical oxidation.
  • the above conductive porous film may be further impragnated with an aniline compound or a water-soluble salt thereof and oxidation-polymerized with said oxidizing agent in a protonic acid-containing reaction medium for a second time so as to cause a further amount of said conductive polymer to precipitate out on the porous film, followed again by rinsing and drying.
  • the resulting porous film can be compressed by means of a roll set to bring the conductive polymer into intimate contact with the film.
  • a rolling operation serves also to adjust the thickness and pore size of the porous film.
  • such a rolling operation may be interposed between a first and a second deposition of the conductive polymer.
  • the electroconductivity of the electroccnductive organic polymer obtained thereby has a close correlation with the composition of the reaction medium containing the protonic acid and the oxidizing agent wherein the oxidative polymerization of an aniline compound is conducted.
  • selection of the composition of the abovs-described reaction medium is very important.
  • the polymer having an electroconductivity exeeding 10 -6 S/cm it is necessary that the molar ratio of protonic acid/potassium dichromate in the reaction medium in which the reaction proceeds should exceed 1.2/1, and is preferably in the range of 2/1 to 50/1.
  • a polymer having a high electroconductivity on the order of from 10 -6 to 10 1 S/cm can be obtained.
  • the electroconductivity of the polymer produced is substantially constant when the molar ratio of protonic acid/potassium dichromate in the reaction medium in which the oxidative polymerization of an aniline compound is carried out is fixed.
  • the polymer having a predetermined degree of elcctrocondugtivity can be obtained with high reproducibility.
  • the amount of potassium dichromate relative to the aniline compound determines the yield of the polymer produced.
  • the electroconductivity of the polymer produced is not substantially affected by the amount of potassium dichromate used in the reaction.
  • the porous film having a predetermined degree of electroconductivity therefore, can be practically obtained in a constant yield when the aqueous solution of the oxidizing agent has a prescribed molar ratio of protonic acid/potassium dichromate and the potassium dichromate is used in at least an equivalent weight relative to the aniline compound.
  • the electroconductive porous film obtained by chemical oxidation generally has an appearance of a green to blackish green color due to the eirectroconductive aniline polymer formed. Generally, this green color gains in brightness as the degree of electroconductivity increases. However, the porous film when oompressed by rolling generally has a glossy blua color.
  • the polymer of an aniline compound formed on the porous film by the chemical oxidation process when its electrical conductivity is more than 10 -6 S/cm, is insoluble in water and moat organic solvents, and, particularly, is substantially insoluble in N,N-dimethylformamide but soluble in 97% concentrated sulfuric acid. This solubility characteristic of the polymer is remarkably different from that of emeraldine.
  • the conductive porous film according to this invention can also be obtained by the electro-oxidation procass.
  • the porous substrate film is held in contact with the ordinary positive electrode, such as a platinum electrode, and an electric currant is passed to cause an electro-oxidation of the aniline compound thereof and thereby precipitate an alectroconductive polymer on the porous film.
  • the porous substrate film has sufficient porosity and wettability to lat the solution of aniline compound flow through when the substrate film as a positive electrode is immersed in the solution.
  • the protonic acid used in this invention is preferably that having an oxidative potential higher than the oxidative potential used in this method.
  • Preferred examples of protonic acids which meet this requirement include hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, tetrafluoroboric acid (HBF 4 ), hexafluorophosphoric acid (HPF 6 ).
  • the prctonic acid should be used in at least an aquimolar amount, generally 1 to 50 molar equivalents, relative to the aniline compound and, at the same time, the anilline compound solution should be subjected to the electro-oxidative polymerization at an electrode potential of at least +1 V relative to the standard calomel electrode.
  • the current density should be 0.01 mA/cm 2 to 1 A/cm 2 .
  • the concentration of the aniline compound in the aniline compound solution be 1% by weight or more. When the concentration is lower than 1% by weight, the resulting polymer tends to have lower molecular weight and lower electroconductivity. Although there is no upper limit in the concentration of the aniline compound in the aniline compound solution, the concentration up to about 50% by weight is generally preferred.
  • the solvent used in this method is preferably such that it dissolves both the protonic acid and the aniline compound and has stable decomposition potential at the oxidation potential used during the electro- oxidativa polymerization.
  • Preferred examples of the solvent include aliphatic lower alcohols such as methanol and ethanol, nitrilas such as acetonitrile and benzonitrile, ketones such as methyl ethyl ketone, and amides such as N,N-dimethylformamide.
  • Water has a deccmposition potential of 1.23 V and, therefore, in some instances, it has a decomposition potential higher than the electro-oxidation potential used in the present invention.
  • the oxidation polymer of the aniline compound having a high molecular weight and high electroconductivity can be produced by adjusting the electro-oxidation potential to +1 V or more.
  • an aniline polymer having a far higher molecular weight and a higher electrcconductivity than those of ameraldine can be produced by carrying cut the electro-oxidation at an electrode potential of +1 V or higher, preferably at an electrode potential in the range of 2 to 10 V.
  • the current density used in the alaetro-oxidation is also an important factor. If the current density is less than 0.01 mA/cm 2 , the polymer produced possesses a low molecular weight, probably in view of the fact that the polymer is soluble in dimethylformamide, and the resulting polymer has a lower alectroconductivity..
  • the aniline compound solution may additionally contain a supporting alectrolyte other than the above-described protonic acid.
  • the supporting electrolyte are metal salts of perchloric acid such as lithium perchlorate and sodium perchlorate and organic salts such as tetrabutyl ammonium perchlorate.
  • salts such as nitrates, sulfates, hydrochlorides, tetrafluoroborntes, and hexafluorophosphates can be used as supporting electrolytes.
  • the conductive porous film produced as above may be immersed again in a solution containing aniline compound and at laast a stoichiometric equivalent of a protonic acid so as to cause an electro-oxidation polymerization of aniline compound and a deposition of the resulting conductive polymer on the porous substrate film.
  • the electroconductive porous film may be subjected to the rolling operation described above. Further, this rolling operation may be interposed between a first and a second deposition of conductive polymer on the film.
  • the electroconductive porous film according to the present invention which is produced by the electro-oxidation, like the electroconductive porous film produced by the chemical oxidation, generally has the appearance of a green to blackish green color due to the electroconductive polymer formed by deposition. Generally, this greon color gains in brightness as the dagree of electroconductivity increases. However, the porous film when compressed by rolling generally has a glossy blue color.
  • the elactroconductive polymer formed on the porous substrate film by the electro-oxidation procass like the polymer by chemical oxidation, has been doped with the protonic acid in the course of electro-oxidation, and the resulting electroconductive porous film generally has an electroconductivity within the range of 10 -3 to 10 -1 S/cm.
  • the elaetroconductive polymer precipitated on the porous film by the electro-oxidation polymerization of aniline or alkylaniline has an electroeonductivity of more than 10 -3 S/cm
  • the polymer is insoluble in water and most organic solvents and, particularly, is substantially insoluble in 97% concentrated sulfuric acid, N,N-dimethylformamide and N-methyl-2-pyrrclidone.
  • the electroconductive porous film according to this invention can also be obtained by depositing an electro-oxidation polymer further on the electroconductive porous film obtained by the chemical cxidation process in an electrolytic cell using the very film as a positive electrode.
  • the elactroconductive porous film of this invention can also be obtained by conducting an electro-oxidation polymerization of an aniline compound using a positive electrode consisting of the electroconductive film according to the chemical oxidation process and an ordinary platinum or other electrode held in intimate contact with said film.
  • the elactroconductive porous film obtainable by a serial application of said chemical oxidation and electro-oxidation of an aniline compound to a porous substrate has particularly stable, high electroconductivity. Referring to this process, it is noted that the electroconductive porous film obtained by the chemical oxidation process has satisfactory wettability with respect to said solution of the aniline compound in the electro-oxidation process.
  • the electrocondustive organic polymoc-obtained by the oxidative polymerization of an aniline compound according to this invention has already been doped with the protonic acid during the polymerization, and, therefore, it possesses a high electroconductivity without requiring an additional doping treatment. Furthermore, this electroconductivity is not altered even after the polymer has been allowed to stand in air for a long time. As compared to conventionally known doped elactroconductive organic polymers, the polymer of this invention has high stability.
  • the electroconductive porous film according to this invention is not only stable but also has a high electroconductivity, it can be advantageously laminated with a dialectric porous film of hydrophobic water-rapellent resin such as fluororesin to provide a membtane for solute separation, as described, e.g., in Japanese Patent Application (OPI) No. 95502/83 (The tarm "CPI” means "published unexamined application”). It can also be advantageously used as an electroconductive porous film for solute separation by applying a high frequency voltage thereto so as to generate microwave vibrations as described, for example, in Journal of Membrane Science, 17, 219-227 (1984) on the membrane surface. It should be understood, however, that the conductive porous film according to this invention is by no means limited to these applications.
  • aniline was oxidation-polymerized with a chemical oxidizing agent under the conditions defined in the text in the absence of a porous substrate film.
  • an aqueous solution of oxidizing agent (molar ratio of protonic acid/potassium dichromate, 7.5/1) was prepared by adding 4.61 g (0.047 mol) of 97% concentrated sulfuric acid in 28.8 g of water and dissolving 1.84 g (0.00625 mol) of potassium dichromate therein. This solution was then added dropwise through a dropping funnel over a period of 30 minutes under stirring to the above aqueous solution of aniline hydrochloride cooled with ice water. During the first 2 to 3 minutes of the dropwise addition, the solution in the flask only colored a yellow color. Thereafter, a green solid was precipitated quickly, whereby the reaction solution turned into a blackish green color.
  • reaction solution was stirred for additional 30 minutes. Then, the reaction mixture was poured into 400 nl of acetone, and the stirring was further continued for 2 hours. Then, the polymer formed in the reaction mixture was separated by filtration, washed by agitation in distilled water and separated by filtration. This washing procedure was repeated until the filtrate became neutral. Finally, the polymer separated by filtration was washed repeatedly with acetone until the filtrate was not colored. The polymer separated by filtration was vacuum dried over phosphorus pentoxide at room temperature for 10 hours to produce an electroconductive organic polymer as a green powder.
  • the polymer obtained above was added to concentrated sulfuric acid having a 97% concentration at room temperature and stirred to determine the solubility.
  • the amount of polymer dissolved therein was 1.2% by weight.
  • a polymer solution in 97% concentrated sulfuric acid in a concentration of 5 g/dl was found to have a logarithmic viscosity number of 0.46 at 30°C.
  • the viscosity of emaraldine and Diamond Black were tested under the same conditions and found to have logarithmic viscosity numbers of 0.02 and 0.005, respectively.
  • an about 120 mg portion of the polymer powder obtained above was pulverized in an agate mortar.
  • the polymer powder was compression molded under pressure of 6,000 kg/cm 2 using a compression molder designed for the preparation of a tablet for the measurement by an infrared spectrophotometer to produce a disk 13 mm in diameter.
  • the disk was tested in the air for electroconductivity by the van der Pauw method (L. J. van der Pauw, Philips Research Reports, Vol. 13, No. 1, R334, February 1958).
  • the electrooonduotivity was found to be 2.0 S/cm.
  • This molded polymer showed substantially the same level of electroconductivity when measured under a vacuum of 10 Torr. When this disk was allowed to stand in the air for four months, the electroconductivity was not substantially altered.
  • the infrared absorption spectrum of the polymer produced above is shown in Figure 1.
  • the infrared absorption spectra of emeraldine and Diamond Black are shown respectively in Figure 2 and Figure 3.
  • the emeraldine was prepared by the method described by A. G. Green et al. (A. G. Green et al., J. Chem. Soc., Vol. 97, p. 23 88 (1910)).
  • the infrared absorption spectum of the polymer of this invention is similar to that of emeraldine, but, at the same time, differs widely in some respects.
  • the absorption spactum of emeraldine clear absorption by the deformation vibration outside the C-H plane due to the mono-substituted benzene is observed at 690 cm -1 and 740 cm -1 .
  • this absorption is not substantially observed, and, instead, strong absorption at 800 cm -1 , indicating the presence of para-substituted benzene, is observed.
  • the difference is particularly apparent in the absorption of large width in the neighborhood of 3,200 to 3,400 cm -1 , the absorption apparently due to a quinolic carbonyl group at 1,680 cm -1 . the region of C-N stretching vibration at 1,200 to 1,300 cm -1 , and in the region below 6 00 cm -1 .
  • the assignment of the infrared absorption spectrum of the polymer of the present invention is as shown below: 1,610 cm -1 (C-N stretching vibration at shoulder), 1,570 and 1,480 cm -1 (C-C stretching vibration in bonzene ring), 1,300 and 1,240 cm -1 (C-N stretching vibration), 1,120 cm -1 (absorption ascribable to dopant; absorption generated at substantially the same position without reference to the kind of dopant), 800 cm -1 (deformation vibration outside C-H plane of para-substituted banzene), and 740 and 690 cm -1 (deformation vibration outside C-H plane of mono-substituted benzene).
  • the infrared absorption spectrum of the polymer obtained by compensating the above-described polymer with ammonia is shown in Figure 4 (B) and that of the polymer obtained by again doping the polymer of Figure 4 (B) with 5 N sulfuric acid is shown in Figure 4 (C).
  • the spectrum of the polymer obtained by repeated doping is virtually identical with the spectrum of the initial polymer shown in Figure 4 (A).
  • the electroconductivity of the polymer obtained by repeated doping is the sane as the initial polymer. The variation of the electroconductivity was 0.45 S/cm before the compensation (A), 1.6 x 10 -8 S/cm after the compensation (B), and 0.31 S/cm after the repeated doping (C).
  • the data clearly indicate that the polymer of the present invention is doped with the protonic acid used during the course of the oxidative polymerization.
  • the electroconductive polymer produced as described above in accordance with this invention was subjected to elementary analysis. Even after this polymer was refined by washing with water and washing with acetone, green powder of anhydrous chromium oxide (Cr 2 O 3 ) was recognized to remain as a residue after the elementary analysis. Thus, the measured values of elementary analysis are shown herein in conjunction with the values determined by calculation based on the total taken as 100. It is noted that the calculated values are well consistent with the theoretical values. The results obtained similarly with respect to the polymer chemically compensated with ammonia are also shown.
  • the amount of sulfuric acid indicated in the theoretical formula was calculated based on the amount of sulfur actually measured in the polymer and the amount of oxygen was stoichiometrically calculated on the basis of the amount of sulfuric acid so determined. In the measured values above the amount of oxygen was calculated on the basis of the amount of sulfuric acid, which was calculated from the measured value of sulfur content.
  • an electroconductive polymer was produced by the electro-oxidation process in the absence of a porous substrate film and the identification of its chemical structure and the evaluation of its physicochemical properties were carried out.
  • the aniline polymer formed on the anode in the above reaction was separated, pulverized, washed by stirring in distilled water, and separated by filtration. The separated polymer was then washed with acetone. The polymer was vacuum dried over phosphorus pentoxide at room temperature for 10 hours to obtain an eleatroaoriauctive organic polymer of this invention as a green powder.
  • Figure 6 shows the cyclic voltamogram in the electro-oxidation of aniline.
  • the solubility of the polymer obtained above in sulfuric acid having 97% concentration at room temperature was determined and was found to be slightly low as compared with that of the polymer obtained by polymerization using chemical oxidation. However, the solubility was increased by ultrasonic treatment to a degree of 1% by weight. Since some insoluble solid material remained in the polymer solution, the solution was filtered through a glass filter to remove the insoluble material, and the filtrate was poured into a large volume of acetone to re-precipitate the polymer which was then separated by filtration, washed with water and dried to obtain a soluble portion of the polymer.
  • the resulting polymer was again dissolved in 97% sulfuric acid at a concentration of 0.5 g/dl and a logarithmic viscosity number of the solution was determined at 30°C which was found to be 0.40.
  • the logarithmic viscosity number of emeraldine and Diamond Black was determined under the same conditions as described above and found to be 0.02 and 0.005, respectively.
  • the logarithmic viscosity was determined by a simplified method, i.e., with respect to a polymer solution obtained by dissolving the polymer in 97% concentrated sulfuric acid at a concentration of 0.5 g/dl and removing a very small amount of insoluble material from the solution of filtration.
  • the logarithmic viscosity number in subsequent Examples was determined with respect to a polymer solution having a polymer concentration slightly lower than 0.5 g/dl since a small amount of insoluble polymer had been removed from the polymer solution, but the difference in the determined viscosity values is substantially on a negligible order. Further, the viscosity determined by this simplified method ensures the minimum viscosity value because this viscosity value is always lower than that determined with respect to a polymer solution having a concentration of exactly 0.5 g/dl, of the re-precipitated soluble polymer.
  • the solution of the re-precipitated polymer must also have a logarithmic viscosity number of 0.1 or more when determined under the same concentration and temperature and thus satisfies the requirement of the present invention.
  • Example 2 About 120 mg of the polymer powder obtained above was molded into a disk in the same manner as Example 1 and its electroconductivity was measurad by the mathod of van der Pauw. The value was 4.1 S/cm. The disk showed nearly the same electroconductivity value as above when determined in a vacuum of 10 -2 Torr. Allowing the disk to stand in air for 4 months caused substantially no change in the electroconductivity.
  • Figure 9 shows the infrared absorption spectrum after ammonia compensation (electrooonductivity 2.3 x 10 -8 S/cm) of the above polymer (electroconductivity 4.1 S/cm), and Figure 10 shows the infrared absorption spectrum of the same polymer after redoping with 5 N hydrochloric acid (electroconductivity 1.21 S/cm).
  • This post-redoping spectrum appears to be substantially identical to the initial spectrum shown in Figure 8 and approximately equivalent to that prior to ammonia compensation. It is, therefore, clear that the electroconductive polymer obtainable by the electro-oxidation process according to this invention has been doped with a protonic acid in the stage of electro-oxidation polymerization.
  • the amount of hydrochloric acid indicated in the theoretical formula was calculated based on the actually found amount of chlorine in the polymer.
  • a porous polytetrafluoroethylene film (Daikin Kogyo K.K., Polyflon Paper®) was immersed in a 10 wt% solution of aniline hydrochloride in ethanol at room temperature for 30 minutes, at the end of which time it was taken out and dried at 60°C for 30 minutes.
  • potassium dichromate potassium dichromate
  • the above electroconductive porous film was immersed as a positive electrode in a 10 wt% aqueous solution of aniline hydrochloride alongside a negative electrode, and a current was passed at an initial electrolytic potential of +2 V (SCE) and a constant current density of 10 mA/cm2, whereby an electroconductive polymer of aniline was further deposited on the porous film. Thereafter, the film was rinsed in distilled water with stirring, and then washed with acetone. The film was further dried in vacuo over phosphorus pentoxide at room temperature for 10 hours to give an electroconductive porous film according to this invention. This film showed an electroconductivity of 2.0 x 10 -1 S/ cm.
  • Example 3 The procedure of Example 3 was repeated except that a porous polysulfone film (Nitto Electric Industrial Co., Ltd., NTU-3100) was used. The procedure gave a porous film having an electroconductivity of 1.7 x 10 -1 S/cm.
  • a porous polysulfone film Nito Electric Industrial Co., Ltd., NTU-3100
  • potassium dichromate potassium dichromate
  • the porous film was rinsed with water and washed with acetone. This procedure was repeated until the acetone wash was colorless and clear. The film was then dried at 60°C for 1 hour. The above procedure was repeated 3 times to give an electroconductive porous film according to this invention. This film had an electroconductivity of 5.5 x 10 -3 S/cm.
  • Example 6 The procedure of Example 6 was repeated except that a porous ethylene-vinyl alcohol copolymer film was employed to produce an electroconductive porous film. This film had an electroconductivity of 3.4 x 10 -2 S/cm.
  • Example 6 The procedure of Example 6 was repeated except that a porous polgetrafluoroethylens film (Daikin Kogyo K.K., Polyflon Papar® was immersed in a 10 wt% solution of aniline hydrochloride in ethanol. The procedure gave an electroconductive porous film having an electroconductivity of 9.2 x 10- 2 S/cm.
  • a porous polgetrafluoroethylens film (Daikin Kogyo K.K., Polyflon Papar® was immersed in a 10 wt% solution of aniline hydrochloride in ethanol.
  • the procedure gave an electroconductive porous film having an electroconductivity of 9.2 x 10- 2 S/cm.
  • Example 6 The procedure of Example 6 was repeated excapt that a porcus polytetrafluoroethylene film sputter-etched in water vapor at 1 x 10- 2 Torr, a discharge voltage of 100 w and a discharge time of 30 seconds, was employed as the substrate film. The procedure gave a porous electroconductive film having an electroconductivity of 3.4 x 10 -4 S/cm.
  • Example 6 The procedure of Example 6 was repeated except that a corona discharge treatment (applied voltage 10 KV) waS carried out in air with a gap of 1 mm for 30 minutes. The procedure gave a porous electroconductive film having an electroconductivity of 7.5 x 10 -5 S/cm.
  • a positive and a negative electrode of platinum metal were set in a 10 wt% aqueous solution of aniline hydrochloride and a polyetrafluoroethylene film (Daikin Kogyo K.K., Polyflon Paper®) pretreated with sodium metal (Junko-sha K.K.) was set in intimate contact with the positive electrode. Then, a current was passed at an initial electrolytic potential of +2.2 V (SCE), a constant current density of 10 mA/cm 2 for 1 hour to deposit a electroconductive aniline polymer on the porous substrate film.
  • SCE +2.2 V

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FR2575586A1 (fr) * 1984-12-28 1986-07-04 Hoechst Gosei Kk Procede pour preparer un article polymere composite conducteur de l'electricite et utilisation de cet article dans la preparation d'une diode a barriere de schottky et d'une electrode a configuration particuliere
EP0195380A2 (fr) * 1985-03-20 1986-09-24 BASF Aktiengesellschaft Procédé de fabrication de mousses électriquement conductrices
EP0195381A2 (fr) * 1985-03-20 1986-09-24 BASF Aktiengesellschaft Matériau composite à base de matières poreuses et de polymères électriquement conducteurs
EP0206133A1 (fr) * 1985-06-12 1986-12-30 BASF Aktiengesellschaft Utilisation de polypyrrole pur déposer de cuivre métallique sur des matériaux non-électriquement conductibles
EP0206414A1 (fr) * 1985-06-21 1986-12-30 Universita' Degli Studi Di Parma Procédé chimique pour conférer des propriétés conductrices, antistatiques et ignifuges à des matériaux poreux
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EP0219063A2 (fr) * 1985-10-09 1987-04-22 Sanyo Electric Co., Ltd Procédé de fabrication d'un matériau conducteur électrique et d'une batterie secondaire utilisant ce matériau conducteur électrique
EP0259813A2 (fr) * 1986-09-10 1988-03-16 BASF Aktiengesellschaft Procédé pour la fabrication d'un matériau composite à partir d'un polymère électroconducteur et d'un matériau céramique
US4740437A (en) * 1985-10-15 1988-04-26 Mitsubishi Petrochemical Co., Ltd. Electrochemical battery having an electrolytically reduced product of a saccharide as the electrode material
WO1989001694A1 (fr) * 1987-08-07 1989-02-23 Allied-Signal Inc. Formes thermiquement stables de polyaniline electriquement conductrice
EP0355518A2 (fr) * 1988-08-03 1990-02-28 E.I. Du Pont De Nemours And Company Articles électroconducteurs
WO1990010297A1 (fr) * 1989-03-01 1990-09-07 Allied-Signal Inc. Formes thermostables de polyaniline electroconductrice
US5171478A (en) * 1991-03-05 1992-12-15 Allied-Signal Inc. Thermally induced chain coupling in solid state polyaniline
WO1993008674A1 (fr) * 1991-10-23 1993-04-29 W.L. Gore & Associates, Inc. Filtre de protection contre les interferences electromagnetiques
US5227092A (en) * 1991-07-10 1993-07-13 Allied-Signal Inc. Process for forming conjugated backbone block copolymers
US5254633A (en) * 1991-07-10 1993-10-19 Allied Signal Inc. Process for the preparation of conductive polymer blends
US5266617A (en) * 1991-04-22 1993-11-30 Allied-Signal Inc. Lewis base catalyzed phase transfer coating process for polyanilines
US5278213A (en) * 1991-04-22 1994-01-11 Allied Signal Inc. Method of processing neutral polyanilines in solvent and solvent mixtures
US5281363A (en) * 1991-04-22 1994-01-25 Allied-Signal Inc. Polyaniline compositions having a surface/core dopant arrangement
US5340499A (en) * 1992-08-11 1994-08-23 Neste Oy Electrically conductive compositions and methods for their preparation
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EP0184367A1 (fr) * 1984-11-30 1986-06-11 Polyplastics Co. Ltd. Procédé de fabrication d'une résine composite électroconductrice
FR2575586A1 (fr) * 1984-12-28 1986-07-04 Hoechst Gosei Kk Procede pour preparer un article polymere composite conducteur de l'electricite et utilisation de cet article dans la preparation d'une diode a barriere de schottky et d'une electrode a configuration particuliere
EP0195380A2 (fr) * 1985-03-20 1986-09-24 BASF Aktiengesellschaft Procédé de fabrication de mousses électriquement conductrices
EP0195381A2 (fr) * 1985-03-20 1986-09-24 BASF Aktiengesellschaft Matériau composite à base de matières poreuses et de polymères électriquement conducteurs
EP0195381A3 (en) * 1985-03-20 1987-04-15 Basf Aktiengesellschaft Composite material and electrically conductive polymers
EP0195380A3 (en) * 1985-03-20 1987-04-29 Basf Aktiengesellschaft Process for manufacturing electrically conductive foam materials
EP0206133A1 (fr) * 1985-06-12 1986-12-30 BASF Aktiengesellschaft Utilisation de polypyrrole pur déposer de cuivre métallique sur des matériaux non-électriquement conductibles
EP0206414A1 (fr) * 1985-06-21 1986-12-30 Universita' Degli Studi Di Parma Procédé chimique pour conférer des propriétés conductrices, antistatiques et ignifuges à des matériaux poreux
EP0218093A1 (fr) * 1985-09-04 1987-04-15 Wacker-Chemie GmbH Polymères avec des liaisons doubles conjuguées
EP0219063A2 (fr) * 1985-10-09 1987-04-22 Sanyo Electric Co., Ltd Procédé de fabrication d'un matériau conducteur électrique et d'une batterie secondaire utilisant ce matériau conducteur électrique
EP0219063A3 (en) * 1985-10-09 1989-03-22 Sanyo Electric Co., Ltd. Electrically conductive material and secondary battery using the electrically conductive material
US4740437A (en) * 1985-10-15 1988-04-26 Mitsubishi Petrochemical Co., Ltd. Electrochemical battery having an electrolytically reduced product of a saccharide as the electrode material
EP0259813A2 (fr) * 1986-09-10 1988-03-16 BASF Aktiengesellschaft Procédé pour la fabrication d'un matériau composite à partir d'un polymère électroconducteur et d'un matériau céramique
EP0259813A3 (fr) * 1986-09-10 1989-10-25 BASF Aktiengesellschaft Procédé pour la fabrication d'un matériau composite à partir d'un polymère électroconducteur et d'un matériau céramique
WO1989001694A1 (fr) * 1987-08-07 1989-02-23 Allied-Signal Inc. Formes thermiquement stables de polyaniline electriquement conductrice
US5069820A (en) * 1987-08-07 1991-12-03 Allied-Signal Inc. Thermally stable forms of electrically conductive polyaniline
US5456862A (en) * 1987-08-07 1995-10-10 Alliedsignal Inc. Thermally stable forms of electrically conductive polyaniline
US5160457A (en) * 1987-08-07 1992-11-03 Allied-Signal Inc. Thermally stable forms of electrically conductive polyaniline
EP0355518A2 (fr) * 1988-08-03 1990-02-28 E.I. Du Pont De Nemours And Company Articles électroconducteurs
EP0355518A3 (fr) * 1988-08-03 1990-12-19 E.I. Du Pont De Nemours And Company Articles électroconducteurs
WO1990010297A1 (fr) * 1989-03-01 1990-09-07 Allied-Signal Inc. Formes thermostables de polyaniline electroconductrice
US5171478A (en) * 1991-03-05 1992-12-15 Allied-Signal Inc. Thermally induced chain coupling in solid state polyaniline
US5278213A (en) * 1991-04-22 1994-01-11 Allied Signal Inc. Method of processing neutral polyanilines in solvent and solvent mixtures
US5266617A (en) * 1991-04-22 1993-11-30 Allied-Signal Inc. Lewis base catalyzed phase transfer coating process for polyanilines
US5281363A (en) * 1991-04-22 1994-01-25 Allied-Signal Inc. Polyaniline compositions having a surface/core dopant arrangement
US5254633A (en) * 1991-07-10 1993-10-19 Allied Signal Inc. Process for the preparation of conductive polymer blends
US5227092A (en) * 1991-07-10 1993-07-13 Allied-Signal Inc. Process for forming conjugated backbone block copolymers
WO1993008674A1 (fr) * 1991-10-23 1993-04-29 W.L. Gore & Associates, Inc. Filtre de protection contre les interferences electromagnetiques
US5506047A (en) * 1991-10-23 1996-04-09 W. L. Gore & Associates, Inc. Electromagnetic interfernce shielding filter
US5340499A (en) * 1992-08-11 1994-08-23 Neste Oy Electrically conductive compositions and methods for their preparation
US5531932A (en) * 1992-08-11 1996-07-02 Neste Oy Metal compound/protonic acid containing electrically conductive compositions and methods for their preparation
US5783111A (en) * 1993-09-03 1998-07-21 Uniax Corporation Electrically conducting compositions

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